Chloromethylation of arylaminopolycyclic quinones



Patented July 14, 1953 CHLOROMETHYLATION OF ARYLAlVIINO POLYCYCLIC QUINONES David I. Randall, Easton, Pa., and Edgar E. Renfrew, Phillipsburg, N. J., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 20, 1950, Serial No. 201,868

4 Claims. (Cl. 260359) This invention relates to vat dye intermediates this invention also may be vatted to produce the of arylaminopolycyclic quinones. More particucorrespondingmethyl derivatives on the fiber. larly it relates to the chloromethylation products Th reduction compounds produced by vatting of arylamino-anthanthrone, -dibenzpyrene quiare considerably brighter than the methyl derivanone, and -pyranthrone compounds. tives synthesized by caustic fusion of these chloro- Vat dyes of arylaminopolycyclic quinones are 5 methyl arylaminopolycyclic quinones. The deinsoluble and not substantive to fabrics as such, veloped dyes are distinguished by their excellent but form a valuable class of dyes due to their fastness propertiesability to pass into solution in a reduced or leuco The, chloromethyl derivative are Produced form which may be applied to the fabric. Alkafrom any of t a y a no-a anthrones, -diline solutions of the reduced or leuco form of benzpyrelle 1 9 or p a ro es such as these dyes possess great amnity for the fiber and 1110110- and l D t t bn may be readily reoxidized by known methods to 1110110- and dl-(anlllno)-anthanthr0ne; m0n0- reform t insomble dy on th fiber, and di-(p chlorophenylamino) anthanthrone;

It has now been discovered that the arylaminomorwd v-1 4 5 b p e e qui-- anthanthrone, arylamino-dibenzpyrene quinone, none; nO- and dl-(anlllno)-dibenzpyrene qu and arylamino-pyranthrone vat dyes may be connone; mOIlO- and l 1 y a no)-diverted to their halomethyl and particularly chlobenzpyrelle q Op-t01uidin0tribromoromethyl derivatives. These chloromethyl derivapymnthl'one; d1 p toluidinodibromo py fi e fo m an extremely Valuable new class of throne; tri-p toluidinobromo-pyranthrone; and: vat dye intermediates. Highly colored soluble "P- d e re-- dyes may be prepared from these intermediates Spondlng 911111110 a l phe ylammo Dyby conversion to the quaternary ammonium and ranthrones. Typical structural formulae for isothiouronium compounds as disclosed in our these startmg mammals copending application Serial No. 201,869, filed on 1) anlilnod v even date herewith. Such conversion products gj gg g dnthanthme may be used to dye cotton directly from aqueous 0 solution. The unconverted chloromethylated arylamino-anthanthrone, -dibenzpyrene quinone, O and -pyranthrone compounds are also valuable 01 as vat dyes themselves. When the chloromethyl derivatives are fused in alkali, the corresponding methyl compounds are produced by reduction of H the chloromethyl groups. H 0}-N The chloromethyl arylamino-anthanthrones, 01 H -dibenzpyrene quinones, and -pyranthrones of i (2) anilino dip-toluidino -dibcnzpyrene quinone p-chlorophen'ylamino anilino tetrap-toluidino }-pyranthrone -chlorophenylamino CH3 N -N GHQ 01 H H 01 The reaction may be represented by the followtain 11.8% chlorine. A product bearing two ing equations: chloromethyl groups has the formula CssI-IzsOzNzClz; R n1x ClGH -OOH 01 R HX-OH l n L Z 2 4 (8 26) Cl=11.6%. Its structure is represented as:

wherein R is an anthanthronyl or dibenzpyrene 0 H quinonyl radical; X is an aryl radical such as E CH3 phenyl or naphthyl; n in an integer from 1 to 2. CH2C1 R(NHX),1 ClCH OCH Ol 1 011120 msoA V r I R(NHXCH2C1)1 Bio-ON (5112mm, H wherein R. is the pyranthronyl radical; X has Example 2 the same value as above, and n1 is an integer from 1 to 4. In a suitable vessel there was placed The anthanthrone, dibenzpyrene quinone, or 940.0 parts sulfuric acid (99.7%). To it there pyranthrone arylamino compound is dissolved was added slowly in concentrated sulfuric acid of at least 95% 103.0 parts di-(p-toluidino)-dibenzpyrene qui- HzFSOr. Dichloro-dimethyl ether is introduced none. When solution was achieved, there was while stirring at room temperature. The reacadded with stirrin tio'n mixture is then stirred for several hours at 40 30.0 p r i hl r m yl e her. The temfrom 30 -30 C. ,After cooling, the reaction mi perature of the reaction mixture was maintained ture is poured'into a large amount of water and at C. for sixteen hours. The mixture, after ice. The precipitate is collected and washed Cooling, was po into a large m u O Wawit w t until e tr L ter and ice. The material which precipitated The invention will be further described with was collected on a filter and washed with water respect to the following examples which are inuntil the washings ran neutral. The dried cake tended to be illustrative of the invention but not We g ed 130 p alysis showed it to conlimitativ'e of its scope. Unless otherwise stated, min lori e- A product bearing two the parts are by weight. chloromethyl groups has the formula Example 1' 50 CasI-IzsOzNzClz; In a suitable vessel there was placed C1=11l6%. Itsstructure is represented as:

ClHzO 0 I II 0 CHzCl 940.0 parts sulfuric acid (99.7%). To it there Example 3 was added slowly In a suitable vessel there was placed 103.0 parts di p toluidino anthanthrone. When solution was achieved, there was added 940'0 parts Sumulc and (997%) To 117 there was added slowly with stirrin 230.0 parfs bischloromethyl ether 165.0 parts tetratoluidino-pyranthrone. When solution had been achieved, there was added perature of the reaction mixture was maintained at 60 for sixteen hours. The mixture, after Wlth stlrrmg cooling, was poured t a huge amount of 276.0 parts bischloromethyl ether. The temt and t at which precipitated was perature of the reaction mixture was maintained collected on a filter and washed with water unat 60 C. for sixteen hours. The mixture, after til the washings ran neutral. The dried cake cooling, was poured into a large amount of waweighed 130 parts. Analysis showed it, t o ter and ice; the material which precipitated was 2,645,645 5 collected on a filter and washed with water unand pyranthrones, having the formula til the washings ran neutral. Analysis of the dried product showed it to contain 13.7% chlol rine. A compound bearing four chloromethyl groups has the formula (NH-XOHzC1),.

C62H4602N4C14;

Cl=13.9%. Its structure is represented as:

o H H H CQN- N@-CH5 01H: CHgCl J) wherein X is an aryl radical, n is an integer ClHz? ([7HzrCl H g H We claim: from 1 to 2, and n is an integer from 1 to 4. 1. Vat dye intermediates selected from the O 2. The vat dye intermediate having the forgroup consisting of anthanthrones, having the mula:

formula H if NQ0H.

(NH-X-OHzC1)n I H201 -(oH1Cl):- 011110 H as l 3 3. The vat dye intermediate having the formula:

olmo 0 H II mo N H NQCH: 4; B101 4. The vat dye intermediate having the formula:

H 11 B30 N N CH,

ClHzC CHaCl H O N N OH: H H H o DAVID I. RANDALL. dibenzpyrene quinones, having the formula EDGAR E RENFREW o References Cited in the file of this patent UNITED STATES PATENTS Number Name Date (CH2CDH 2,531,464 Randall et a1 Nov. 28, 1950 2,531,465 Randall et a1 Nov. 28, 1950 FOREIGN PATENTS Number Country 7 Date 612,222 Great Britain Nov. 10, 1948 613,983 Great Britain Dec. 7, 1948 7 623,997 Great Britain May 26, 1949 623,998 Great Britain May 26, 1949 

1. VAT DYE INTERMEDIATES SELECTED FROM THE GROUP CONSISTING OF ANTHANTHRONESM HAVING THE FORMULA 